Rheol Acta (2008) 47:425–433
DOI 10.1007/s00397-008-0265-4
ORIGINAL CONTRIBUTION
Rheology of carbon nanofiber-reinforced polypropylene
Simona Ceccia & Dino Ferri & Daniela Tabuani &
Pier Luca Maffettone
Received: 5 June 2007 / Revised: 21 December 2007 / Accepted: 28 January 2008 / Published online: 15 April 2008
# Springer-Verlag 2008
Abstract The rheological properties of two different nano-
composite systems consisting in the dispersion of carbon
nanofibers (CNFs) in polypropylene are investigated. The
nanoreinforced systems were identically prepared with two
CNFs that differ only in the length of the fibers being
otherwise identical to analyze the effect of fiber aspect
ratio. Linear dynamic viscoelasticity and the steady-state
rheology of the two different nanocomposites are presented.
The system reinforced with CNFs with larger aspect ratio
shows several rheological features that resemble peculiar-
ities of rodlike polymers in the nematic liquid crystalline
phase.
Keywords Carbon nanofiber . Viscosity . Normal stresses .
Linear viscoelasticity
Introduction
Carbon nanofibers (CNFs) represent a viable solution to the
preparation of polymer nanocomposites with improved
S. Ceccia : D. Tabuani
Centro Ingegneria Materie Plastiche,
Viale T. Michel 5,
15100, Alessandria, Italy
D. Ferri
Centro Ricerche “Claudio Buonerba”, Polimeri Europa,
Via Taliercio 14,
46100, Mantova, Italy
P. L. Maffettone (*)
Dipartimento di Ingegneria Chimica Università Federico II Napoli,
Piazzale V. Tecchio 80,
80125, Napoli, Italy
e-mail: pierluca.maffettone@unina.it
mechanical, thermal, and electrical properties (e.g., Yang
et al. 2007; Kelarakis et al. 2006; Gao et al. 2006; Choi et
al. 2005; Xu et al. 2004). CNFs have multiple concentric
walls, with diameter ranging from 70 to 200 nm and length
50–100 μm. They are not continuous tubes as the graphene
cylinders, and they are not parallel to the fiber axis. Rather,
they show a 20° angle with respect to fiber axis in a Dixie
cup arrangement terminating at the wall of the next outer
tube (Kang et al. 2006). The characteristic nanoscopic
dimension together with a relatively low cost and the easy
incorporation into polymers make CNFs an obvious
candidate for the production of high performance light
materials. Several recent papers show the benefits of the
addition of CNFs in polymer matrices in terms of
mechanical, electrical, and thermal properties. For example,
Kumar et al. (2002) showed that fibers from PP/CNF
composites can be spun using conventional equipment, and
possess superior modulus and compressive strength with
respect to the pure polymer at only 5 wt% of CNFs. Such
an improvement was obtained by dispersing as received
CNFs into the polymer via melt processing. Sandler et al.
(2003) studied nanoreinforced fibers of a semicrystalline
high-performance poly(etheretherketone) containing up to
10 wt% CNFs. The carbon nanofibers were found to be
well aligned with the direction of flow during processing,
and, correspondingly, nanocomposite stiffness, yield stress,
and fracture strength improved with respect to neat
polymer. Upon addition of nanofibers, a significant increase
of the degree of crystallinity of the matrix was also
observed. Gauthier et al. (2005) studied the reinforcement
of rubbery matrices by CNFs and showed that the
mechanical performances revealed a linear increase of the
modulus measured above and below the glass transition
temperature for nanofiber content up to 10 wt%. In the case
of an epoxy matrix, the ultimate stress and strain were also
426
largely increased, even for very low-fiber content (1 wt%).
Shen et al. (2006) showed that CNFs can be used both as
nucleant and reinforcement for polystyrene (PS) foams. The
inclusion of CNFs exhibited a substantial impact on the
morphology and properties of PS foams by decreasing
the cell size and increasing the cell density. A substantial
strength enhancement of PS foams due to the incorporation
of CNFs was experimentally observed.
The rather common observation of improvements of the
mechanical properties of CNF-reinforced plastic products is
generally related to the formation of a microstructure. In the
molten state, such microstructure can be easily probed with
rheological experiments. Linear and nonlinear viscoelastic
properties provide important information on the dispersion
of the filler in the matrix, on the concentration and size
distribution of the filler, and its wettability. Only few and
very recent papers, however, were devoted to the rheolog-
ical characterization of CNF-reinforced polymers (Lozano
et al. 2004; Xu et al. 2005; Wang et al. 2006). Lozano et al.
(2004) characterized the linear dynamic viscoelasticity of
CNF nanoreinforced HDPE. They noted a monotonic
increase of G’ and G” moduli both with frequency and
concentration, with the appearance of a solid-like plateau at
low frequencies at loadings ≥20 wt%. Xu et al. (2005)
presented a very detailed study on samples of CNFs in
glycerol/water to analyze the effects of different purification
techniques (sonication and acid treatment). Nanocompo-
sites from as-received nanofibers showed large aggregates
(mm to cm), whereas sonication significantly reduced
aggregate dimensions (50 μm), and an acid treatment
improved the dispersion but at the cost of shortening the
CNFs. A solid-like behavior of the moduli was found for
loadings larger than 3 wt%. Xu et al. (2005) also modeled
the nanocomposite systems with either elastic or rigid
dumbbells in a Newtonian solvent with isotropic or
anisotropic hydrodynamic drag, with or without hydrody-
namic interaction. They found that the elastic model with
anisotropic hydrodynamic drag and negligible hydrody-
namic interaction successfully captures the rheological
behavior observed in their experiments. Very recently, the
same research group (Wang et al. 2006) presented an
analysis on shear rheology of nanofiber/polystyrene com-
posites. The focus was on the effect of the preparation
technique as captured by rheological measurements. It was
shown that melt blending strongly reduces the length of the
fibers with respect to solvent-casting preparation. A general
monotonic increase of both G’ and G” was observed. The
melt phase of solvent-cast composites with higher CNF
concentrations exhibits a plateau of the elastic modulus at
low frequencies, an apparent yield stress, and large first
normal stress difference, N1, at low strain rates. The authors
ascribed such features to contact-based network nano-
structure which forms in the presence of longer CNFs.
Rheol Acta (2008) 47:425–433
Also, the experimental results were well described by a
model similar to those commonly adopted to describe fiber
suspensions in viscoelastic liquids.
In the present work, we characterize the rheological
response of two different nanocomposite systems consisting
in the dispersion of CNFs in polypropylene. The nano-
reinforced systems were obtained with two CNFs that differ
only for the length of the fibers being otherwise identical
and identically prepared. In such a way, a clear analysis of
the relevance of the fiber aspect ratio can be addressed. The
linear dynamic viscoelasticity and the steady state rheology
of the two different nanocomposites are presented. As it
will be shown, the rheological characterization of system
reinforced with CNFs with larger aspect ratio shows several
features that resemble peculiarities of rodlike polymers in
the nematic liquid crystalline phase. This phenomenology is
similar to that recently observed for carbon nanotubes,
which are considered as a type of highly conjugated, rigid-
rod macromolecules. Carbon nanotubes have shown inter-
esting similarities with “rigid-rod” macromolecular systems
(Song and Windle 2005). Indeed, it was reported that
carbon nanotubes can form nematic liquid crystalline
phases (Song et al. 2003; Davis et al. 2004; Song and
Windle 2005). The existence of a nematic phase could of
course lead to interesting final properties as large-scale
alignment could be achieved under processing conditions.
Materials and methods
The nanoreinforced polymer was prepared with a homo-
polymer commonly used to produce injection-molded
products (Moplen HP400R, Basell). The relevant polymer
properties are reported in Table 1.
Two different nanofibers produced by Applied Sciences
Inc were dispersed in the matrix: PR-24 LHT HD (High
Density) and PR-24 LHT LD (Low Density). The HD and
LD designations do not refer to the density of the individual
fiber but to the bulk density of the carbon nanofibers. The
bulk, or aggregate density, of the nanofiber is controlled by
altering the mixing intensity and duration of the debulking
process. The debulking process reduces the length of the
individual fibers, with high density fiber having shorter
fiber lengths than the low density fiber. The producer states
Table 1 Properties of the polymeric matrix
Property Method Value Unit
Density (23 °C) ISO 1183 0.905 g/cm3
Melt flow rate ISO 1133 25 g/10 min
(230 °C/2.16 kg)
Melt volume flow rate ISO 1133 34 cm3/10 min
(230 °C/2.16 kg)
Rheol Acta (2008) 47:425–433
Table 2 Relevant properties of the CNFs
Name N2 surface area, Moisture Iron content
(m2/gm) (%) (PPM)
PR-24 LHT HD 35–45 <5 <14,000
PR-24 LHT LD 35–45 <5 <14,000
that typically, the fiber length in the low density product is
100–200 μm, while the fiber length in the high density
product is 50–100 μm (Burton, personal communication).
The relevant parameters of the nanofibers are reported in
Table 2.
The dispersion of nanofibers in polypropylene was
achieved by melt compounding as-received CNFs with the
polymeric matrix in a Brabender internal mixer. The
internal mixer consisted of a heated chamber with a volume
of 55 cm3. The chamber was closed between two plates: a
fixed plate with two counter-rotating mini-screws (maxi-
mum rate 200 rpm), and a mobile one with the hopper and
the chamber. Mixing was performed at 180 °C, 60 rpm, for
10 min. Processing conditions were chosen to optimize
nanofiber dispersion and to minimize matrix degradation.
Both nanocomposite systems were prepared following the
very same procedure. The melt compounding preparation is
expected to cause the breakage of nanofibers, thus altering
their nominal properties. Transmission electron microscopy
images recorded on CNF extracted by dissolving PP in
Xylene (not shown here) showed that the ratio between
average LD-CNF and HD-CNF length is practically
preserved after preparation.
Five different compositions were prepared with HD
nanofibers as reported in Table 3; nine compositions were
prepared with LD CNFs as reported in Table 4.
Scanning electron microscopy (SEM) imaging was
obtained by means of a LEO 1450 VP instrument on cryogenic
fracture surfaces. SEM micrographs showed that a rather
uniform dispersion was generally obtained, but some aggre-
gates were still present. Similar state of dispersion character-
izes materials prepared with HD-CNF and LD-CNF. An
example is reported in Fig. 1. The fiber length distribution
was affected by the mixing process, and a reduction of the
fiber aspect ratio was observed for both CNFs even though
no quantitative assessment was carried out.
The preparation of the nanoreinforced materials could
affect the matrix properties by inducing some thermome-
Table 3 Compositions of HD-based nanocomposites
Unit Fiber concentration
wt% 0.50 1.00 3.00 6.00 10.0
vol% 0.27 0.53 1.62 3.29 5.58
427
PAH content Diameter Length Nominal aspect
(mg PAH/g fiber) (nm) (μm) ratio
<1 100–200 50–100 250–1,000
<1 100–200 100–200 500–2000
chanical degradation. Thus, for the sake of comparison, the
pure polypropylene matrix MPHP400R was also subjected
to the same thermal and mechanical treatments as the
nanocomposites to have a consistent reference matrix.
The samples were rheologically characterized with
different instruments. The linear viscoelastic storage moduli
were measured in shear at 25 °C with a Rheometrics
Mechanical Spectrometer (RMS) model 800 at a frequency
of 1 Hz using the torsion rectangular geometry. The
instrument was equipped with a force rebalance transducer
able to detect torques within the range 0.02–20 N. The
actuator was an air bearing motor with strain amplitude of
0.05–500 mrad and a rotation angular frequency varying
between 10–3 and 102 rad/s. The specimens were compres-
sion-molded at about 210 °C and recovered as rectangular
60×2×8 mm stripes to fit the RMS tools. The temperature
was stable within 0.2 °C over the range used in this study.
Strain sweeps were performed with strain amplitudes
ranging from 0.01 to 1.4. The shear storage moduli reported
in the following are those measured in the linear viscoelas-
tic response region. All tests were performed in N2
atmosphere.
For dynamic linear viscoelasticity of the melt, the
samples were compression-molded at 210 °C under a
pressure of 20 MPa and recovered as 25 mm diameter
disks to fit the RMS tools. The linear viscoelastic functions
were measured in the RMS using the parallel plate
geometry (diameter 25 mm and gaps between 0.6 and 1
mm). Isothermal frequency scans were performed in the
range between 10−1 and 102 rad/s. The temperature was
stable within 0.2 °C over the range used in this study. Strain
sweeps were previously performed to investigate the linear
viscoelastic response region, and time sweeps were also
performed to test the thermal stability of the samples. All
tests were carried out in N2 atmosphere.
The steady-state shear rheology was investigated at 210 °C
using the rotational rheometer (RMS800) in the low shear rate
region and a capillary rheometer (Göttfert Rheograph 2002) in
the high shear rate region. Step rate experiments were
performed under a N2 atmosphere with the cone-plate
geometry (cone angle 0.1 rad) in the shear rate range [0.02,
20 s−1]. The temperature was stable within 0.2 °C over the
range used for the rotational rheometer tests. The measure-
ments with the capillary rheometer were performed in the
shear rate range [1, 5000 s−1] and corrected for non-
428
Table 4 Compositions of LD-based nanocomposites
Unit Fiber concentration
wt% 0.25 0.50 1.00 1.50
vol% 0.13 0.27 0.53 0.80
Newtonian effects (Rabinowitsch correction). A round hole
capillary was used with L/D=30 (diameter=1 mm, length=
30 mm, entry angle=180°). This L/D value was large enough
to allow to neglect the Bagley correction. The rheometer was
equipped with a pressure transducer able to detect pressures
up to 1.4×108 Pa.
Experimental results
Linear viscoelasticity
In the molten state, a strain sweep was performed to
determine the limits of linear viscoelastic regime. At an
angular frequency 5=6.28 rad/s and at a temperature T=
210 °C, the pure reference matrix showed a linear response
up to 100% strain, which was the largest applied strain.
Figure 2 shows a reduction of the linear range for the
nanoreinforced material with HD fibers starting from 3 wt%,
while for the LD samples starting at 1.5 wt%.
Frequency sweep test—HD carbon nanofibers
Frequency sweep tests at T=210 °C were performed with
angular frequencies ranging from 0.1 to 100 rad/s. The
presence of HD-CNFs produces a small increase in moduli
up to 3 wt%, where G’ and G” data follow closely the
unfilled reference matrix data (PP) throughout the frequen-
cy range as shown in Fig. 3. A “hesitation” is found
between 0.5 and 1 wt% as the two data sets nearly
Fig. 1 A SEM image of HP400R +3 wt% of HD-CNFs
Rheol Acta (2008) 47:425–433
2.00 3.00 4.50 6.00 10.0
1.07 1.62 2.45 3.29 5.58
superimpose. It can be noted that G’ increases more than
G” in this concentration range. At low concentrations, the
storage modulus enhancement is usually attributed to
stiffness imparted by the solid particles that allow efficient
stress transfer, which is mainly controlled by the matrix/
fiber–matrix interface. At larger loadings (6 and 10 wt%),
the moduli increase steeply. Thus, above a threshold value
(in this case above 3 wt%), a pseudo-solid-like behavior is
observed at low frequencies, i.e., G’ and G” data show the
appearance of a plateau, suggesting the formation of some
interconnected nanofiber network within the matrix. It is
well known from the literature that the interconnected
structures of anisometric fillers result in an apparent yield
stress which corresponds, in dynamic measurements, to the
plateau of G’ or G” at low frequencies (Shenoy 1999;
Utracki 1986; Dealy and Wissbrun 1999). This effect is
more pronounced in G’ than in G”. This is in accordance
with theoretical expectations and experimental observations
for fiber-reinforced composites (Shaffer et al. 1998;
Pötschke et al. 2002; Lozano et al. 2004). Indeed, as the
nanofiber content increases, nanofiber–nanofiber interac-
tions begin to dominate, eventually leading to percolation
and to the formation of some interconnected structure.
The magnitudes of the complex viscosity, η*, of the
reference matrix and composites with different HD-CNF
content are shown in Fig. 4. Of course, consistently with
moduli data, at small loadings (<3 wt%), the presence of
solid particles perturbs the normal flow of polymer, and, as
usually observed in dilute suspensions of rigid particles, the
10
LD samples
HD samples
1
Strain
0.1
0.01
0.001
1 10
%wt CNF
Fig. 2 The limiting strain for linear viscoelastic response (T=210 °C,
5=6.28 rad/s)
Rheol Acta (2008) 47:425–433 429

Fig. 3 Effect of CNFs HD on 5

10
5
10
the linear viscoelastic response a b
(T=210 °C). a Storage modulus; 4
10
b Loss modulus 4
10
3
10

G" (Pa)
G' (Pa)
3
10
2
10
PP PP
HD 0.5% HD 0.5%
1 2
10 HD 1% 10 HD 1%
HD 3% HD 3%
HD 6% HD 6%
0
10 HD 10% HD 10%
1
10
-1 0 1 2 -1 0 1 2
10 10 10 10 10 10 10 10
ω (rad/s) ω (rad/s)

magnitude of the complex viscosity of the filled system
increases. Up to 3% loading, the norm of the complex
viscosity of HD-CNF samples shows a dependence on the
frequency similar to that of pure matrix, revealing a
Newtonian plateau at low frequencies. A simple vertical
shift is observed as the concentration increases as normally
observed with conventional microcomposite systems, con-
sistently with what is observed for G’ and G”. Above 3 wt%,
η* data do not show the Newtonian plateau at low
frequencies anymore, and yield stress appears.
Frequency sweep test—LD carbon nanofibers
A much richer behavior is observed in the case of fibers with
larger aspect ratio, i.e., with the LD-CNF nanocomposites. In
this case, the frequency sweep measurements are shown in
Fig. 5 (for the sake of clarity, only a selection of
concentrations is plotted). It is apparent that the increase of
both moduli is much larger than that observed with HD-
CNFs at the same loading (see Fig. 3), and the pseudo-solid-
like plateau is observed at lower concentrations (it already
appears above 2 wt%). At the lower nanofiber concentra-
4
10
PP
HD 0.5%
HD 1%
HD 3%
HD 6%
HD 10%
|η*| (Pa s)
tions, the magnitude of the complex viscosity increases with
respect to the reference matrix preserving the Newtonian
plateau at low frequencies (Fig. 6). Above 2 wt%, η* data do
not show the Newtonian plateau anymore, and yield stress
appears. This evidence confirms the existence of a
threshold concentration value between 2 and 3 wt%, mar-
king the onset of a solid-like behavior at low frequencies.
The enhancement of moduli due to the presence of LD-
CNF is significantly higher at lower frequencies, and the
increase is more pronounced in the storage modulus. Thus,
as it could be expected, the system with lower aspect ratio
(HD-CNFs) shows a larger percolation concentration with
respect to the system with larger aspect ratio (LD-CNFs). A
similar effect of the aspect ratio was found by Kitano et al.
(1984) with polyethylene melts filled with glass fibers. The
very recent data proposed by Wang et al. (2006) also show
the same dependence on the fiber aspect ratio.
The most striking feature, however, is the distinct
nonmonotonic dependence of the moduli on the filler
concentration. Indeed, at a fixed frequency, as the loading
increases from 0% (pure polymer), both moduli first increase
(at 0.5%) then decrease (at 1.5%), and then they increase
again (at 3%). This feature is even more evident in the
magnitude of complex viscosity data plotted in Fig. 6.
Figure 7 shows the variation of the shear storage
modulus of composites at 25 °C. It is apparent that both
inclusions improve the modulus as the filler concentration
increases, but the effect of the LD-CNFs is substantially
larger. Again, the difference between the two set of data can

• 3
10 be ascribed to the different aspect ratio of the inclusions.
As already observed in linear viscoelastic data taken in
the molten state, an interesting feature of these data is the
presence of a relative maximum at low composition. This
maximum is clearly visible in the case of LD-CNFs, while
it is hardly detectable in the HD-CNF samples.
2
10
0 1 2
10 10 10 Steady-shear tests
ω (rad/s)
Fig. 4 The magnitude of the complex viscosity (T=210 °C) for the Steady-shear tests were performed only on the LD-CNF
HD-CNF nanocomposites nanocomposites in view of their peculiar response in linear
430 Rheol Acta (2008) 47:425–433

Fig. 5 Effect of LD-CNFs on 5

10 10
5

the linear viscoelasticity a b

(T=210 °C). a Storage modulus; 4
10
b Loss modulus 10
4

3
10

G" (Pa)
G' (Pa)
3
10
2
10
PP PP
LD 0.5% LD 0.5%
1 2
10 LD 1.5% 10 LD 1.5%
LD 3% LD 3%
LD 6% LD 6%
0
10 LD 10% LD 10%
1
10
-1 0 1 2 -1 0 1 2
10 10 10 10 10 10 10 10
ω (rad/s) ω (rad/s)

viscoelasticity. The experiments were carried out in a strain-
controlled rotational rheometer at lower shear rates [0.02–
20 s−1] and in a capillary rheometer at higher shear rates
[1–5,000 s−1]. The viscosity data obtained with the two
instruments perfectly overlap at intermediate shear rates.
At low shear rates, the addition of LD-CNF to the
polymer matrix produces a general increase of the viscosity
with respect to that of the matrix. At lower concentrations, a
Newtonian plateau is found at low shear rates, while at
higher fractions, yield stress appears at low shear rates (see
Fig. 8b). Nanocomposites with solid fraction above 2 wt%
exhibit strong shear thinning throughout the investigated
shear rate range. Again, data suggest the formation of some
network structure. Shear thinning behavior of the viscosity
can be associated at low shear rates to the breakdown of the
network structure and at large shear rates to the possible
alignment of the fibers along the flow direction.
At higher shear rates, the effect of the filler on the
viscosity is reduced in magnitude, and the nanocomposite
viscosity tends to the matrix viscosity. The significant
decrease in viscosity at higher shear rates shows that the
difficulty of processing nanofiber systems should not be an
issue with those under investigation here.
5
10
PP
The most peculiar behavior is the nonmonotonic depen-
dence of the viscosity on the CNF fraction at low concen-
trations, which parallels that observed in the linear
viscoelastic functions. At low shear rates, a distinct New-
tonian plateau is visible for loading up to 1.5 wt%. Here, the
zero shear viscosity of nanocomposites first increases then
decreases, thus confirming the linear viscoelastic features.
This feature is apparent in Fig. 9, where the zero shear
viscosity for the LD-CNF systems that show a Newtonian
plateau at low shear rates is plotted as a function of
nanofiber content.
The trend of the viscosity reported in Fig. 9 is very
similar to that observed in systems showing anisotropic
mesophases, such as lyotropic rodlike polymers showing
nematic liquid crystalline phases (see the Discussion
section).
The similarity with such systems appears to be even
stronger if the first normal stress difference is considered.
The first normal stress difference, N1, was measured during
start up of steady-shear tests with the rotational rheometer
equipped with cone and plate fixture. Special care during
sample loading was necessary to have reproducible data. A
0.90
0.85 T=25∞C
shear storage modulus (GPa)

LD 0.5%
LD 1% 0.80
LD 1.5%
LD 2% 0.75
4
10 LD 3%
0.70
|η*| (Pa s)

• LD 6%
LD 10%
0.65

3 0.60
10
0.55
PP+LD CNF
0.50 PP+HD CNF
PP
2
10 0.45
-1 0 1 2 0 1 2 3 4 5 6 7 8 9 10 11
10 10 10 10
ω (rad/s) CNF LD (wt %)
Fig. 6 Effect of LD-CNFs on the magnitude of complex viscosity Fig. 7 Shear storage modulus at T=25 °C for LD and HD CNF
(T=210 °C) nanocomposites
Rheol Acta (2008) 47:425–433 431

Fig. 8 Viscosity for the refer- PP PP

ence matrix (PP) and nanocom- LD 0.25% LD 0.25%
posites with different LD-CNF 4
10 LD 0.5% 4
LD 0.5%
LD 1%
10
loadings (T=210 °C). a Viscos- LD 1%
LD 1.5% LD 1.5%
ity versus shear rate; b Viscosity LD 2%

Viscosity (Pa•s)

Viscosity (Pa•s)
LD 2%
LD 3%
versus shear stress 3
10 LD 6%
3
10
LD 3%
LD 6%
LD 10% LD 10%

2 2
10 10

1
a b
1
10 10
-2 -1 0 1 2 3 4 1 2 3 4 5
10 10 10 10 10 10 10 10 10 10 10 10
-1
shear rate (s ) shear stress (Pa)

waiting time after loading was used to eliminate the effects
of loading history. During this waiting time, the normal
force generated by sample squeezing was monitored up to
full sample relaxation. The highest CNF concentrations led
to a maximum waiting period of 1 h before testing.
Figure 10 shows the N1 transient for a sample with 6 wt%
LD-CNF at two different shear rates (5 and 10 s−1). The
shear rate is stepped up after the first 100 strain units. For
the sake of comparison, the transients of the unfilled PP at
the same shear rates are also presented in the figure. The
effect of the filler with respect to the unfilled sample is
apparent. A clear initial overshoot followed by an under-
shoot and long and oscillating N1 transients were observed
for LD-CNF samples above 1 wt%.
Figure 11 reports the average steady state value of the
first normal stress difference as function of the shear rate.
Normal stress signals become measurable only at high
shear rates. At larger LD-CNF composition (6 and 10 wt%),
N1 attains negative steady-state values.
Both long oscillating transient and negative first normal
stress difference are typical features of lyotropic rodlike
polymers in the nematic phase.
Discussion
The viscosity and normal stress data observed with our LD-
CNF nanocomposites at 210 °C share several peculiarities
of lyotropic nematic polymers. The introduction of filler
within a polymeric matrix alters the flow properties of the
system, and usually the processing becomes more difficult.
This aspect is easily verified with rheological characteriza-
tion, as a distinct increment of viscosity is usually observed.
This is not observed, however, in the case of solutions of
rodlike polymers showing a nematic liquid crystalline state
(Doi and Edwards 1986). In that case, in fact, as the rodlike
particle fraction increases, the zero shear viscosity first
increases, then, when a critical concentration is reached, a
distinct decrement of the viscosity is observed. This
evidence is related to the transition from an isotropic state
to the liquid crystalline phase characterized by a significant
degree of orientational order. Indeed, in the liquid crystal-
line state, the rodlike molecules are more free to diffuse as
the overall alignment reduces the effects of entanglements
thus increasing the rotational diffusivity. As the concentra-
tion of rodlike molecules further increases, the zero-shear

1500
PP 5s-1
PP 10s-1
LD6% 5s-1
LD6% 10s-1

1000
N1 (Pa)

500

0
0 50 100 150 200 250
Strain
Fig. 9 The plateau viscosity at low shear rates versus the LD-CNF Fig. 10 Transients of the first normal stress difference for unfilled PP
composition (T=210 °C) and for LD-CNF 6 wt% plotted versus strain (T=210 °C)
432
3500 PP
LD 0.5%
3000
LD 1%
LD 1.5%
2500 LD 2%
LD 3%
2000 LD 6%
N1 (Pa)
LD 10%
1500
1000
500
0 above a critical concentration under quiescent conditions,
-500
10
-1 0
10 10
1 evidence is at the moment available on the possible
-1
Shear rate (s )
Fig. 11 First normal stress difference measured for LD-CNF nano-
composites subjected to steady shear flows (T=210 °C)
viscosity eventually starts to increase again as the ordering
beneficial effects cease the way to the progressive increase
of viscous drag due to the relative motion between solvent
and rods. A viscosity decrease with increasing fiber fraction
was already seen in the PET/CNF nanocomposites studied
by Ma et al. (2003), but no explanation was suggested for
the peculiar behavior. Similar features have been observed
in a system containing multiwalled carbon nanotubes in
aqueous solvent (Song et al. 2003; Song and Windle 2005)
and in single-wall nanotubes in superacid (Davis et al.
2004). In these papers, the fact was explained by
considering that the phase behavior of carbon nanotube
systems show many parallels with that of lyotropic
nematogenic rodlike polymer solutions.
Another peculiarity of liquid crystalline polymers is the
appearance of negative first normal stress difference under
shear at intermediate shear rates (e.g., Kiss and Porter
1978). Such a behavior is rather uncommon and is now
well understood (Marrucci and Maffettone 1989; Larson
1990). Its origin lays in the disordering effect of shearing
flow onto the orientational order of a nematic phase.
Negative first normal stress differences have been measured
also on single-wall nanotubes in superacid (Davis et al.
2004), thus corroborating the LCP similarity of that
material on attractive emulsions (Montesi et al. 2004), and
on nanotube suspensions (Lin-Gibson et al. 2004). In the
two latter cases, however, the occurrence of negative
normal stresses was related to vorticity alignment of
macroscopic aggregates.
Finally, as far as the transient behavior of first normal
stress difference is concerned, the evidence of long
oscillating transients is again very similar to the response
of ordered mesophases. Indeed, oscillations in N1 have
been found for lyotropic nematic solutions of poly(benzyl
glutamate) (PBG), hydroxypropylcellulose, and other lyo-
Rheol Acta (2008) 47:425–433
tropic as well as thermotropic liquid crystalline polymers
(e.g., Quijada-Garrido et al. 2000 and references therein).
All these nonlinear features were here observed for the
case of a large aspect ratio CNF system, thus suggesting the
possible formation of a mesophase. Although intriguing for
its processing implications, this parallel should be carefully
examined in view of an important difference between the
two systems. Indeed, it seems now undisputable that the
nanofibers are non-Brownian objects (e.g., Wang et al.
2006). On the contrary, rodlike polymers are Brownian, and
they spontaneously form an ordered nematic phase. No
formation of nanofiber-ordered phases at equilibrium. It
should be mentioned, however, that under flow condition,
nanofibers can behave as pseudo-Brownian objects, rota-
tional diffusion being caused by casual collisions (Folgar
and Tucker 1984).
A final comment is in order. We did not observe any
peculiar feature with the HD-CNF sample. Furthermore,
Wang et al. (2006) do not mention any of these phenomena
for both polystyrene-CNF nanocomposites they investigat-
ed. These three systems (our HD-CNF, and the systems
investigated by Wang et al.) are characterized by a lower
fiber aspect ratio with respect to that of our LD-CNF
system. In our opinion, “nematic-like” response can be
observed if the fiber aspect ratio is large enough to promote
the ordering effects at relatively low compositions. If this is
not the case, the possible formation of a network structure
hinders the manifestation of orientational ordering.
Final comments
In this paper, we have studied the rheological behavior of
two carbon nanofiber nanocomposites. The systems differ
only for the fiber aspect ratio, being otherwise equivalent.
The nanofibers are dispersed in a polymer matrix via melt
compounding. Linear viscoelasticity shows the formation
of a network structure for both systems for compositions
above a critical value. The nanocomposite characterized by
CNF with larger aspect ratios shows a more pronounced
increase of moduli and a lower critical composition.
Nonlinear rheology showed that the system with larger
nanofiber aspect ratio has several peculiarities similar to
polymers in the nematic phase. This aspect can have
interesting practical implications in the applications, as
ordered state is usually characterized by exceptional
mechanical properties.
Acknowledgements This work was supported by FIRB MAPIO
NANO.
Rheol Acta (2008) 47:425–433
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